The fundamentals of applying electrospray ionization mass spectrometry to low mass poly(methyl methacrylate) polymers

McEwen, Charles N.; Simonsick, William J.; Larsen, Barbara S.; Ute, Kaichi; Hatäda, Koichi

doi:10.1016/1044-0305(95)00476-t

Cited by 72 publications

(69 citation statements)

References 25 publications

(12 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Consequently, the spectra are complicated and more difficult to interpret. 31 The upper mass range of the quadrupole analyser used is m/z 4000, which restricts the analysis of singly charged polymer species to low-molecularweight samples.…”

Section: Discussionmentioning

confidence: 99%

A Study of Cation Attachment to Polystyrene by Means of Matrix-assisted Laser Desorption/Ionization and Electrospray Ionization-Mass Spectrometry

Deery

Jennings

Jasieczek

et al. 1997

Rapid Commun. Mass Spectrom.

105

View full text Add to dashboard Cite

A range of metal cations has been shown, by means of matrix assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) mass spectrometry, to form adduct complexes with polystyrene. Both MALDI and ESI mass spectra contain adduct ion peaks corresponding to [ Polymers such as PEG and PMMA, which contain basic oxygen atoms in the repeat unit, interact effectively with alkali metal ions such as Li + and Na + . It has been shown, by means of molecular modelling calculations, that the lowest energy conformer structure of [PEG + Na] + (where the degree of polymerisation, n, is 9) involves multiple oxygen atoms which are coordinated about the Na + centre. 37 Conversely, polystyrene is a hydrocarbon and contains no basic atoms to which metal ions may bind. It is thought that the most likely site of cation attachment along the polystyrene chain is the phenyl ring in the repeat unit. 38Previous MALDI-MS studies have shown that the molecular weight (MW) distribution that is observed in the mass spectra of polar polymers is dependent on which alkali metal salt is used to dope the polymer and matrix mixture. [39][40][41][42] For example, it has been demonstrated that the value of the number-average molecular weight (M n ) (Eq 1) of PET 43 and PMMA 39 increases with increasing size of cation. It is thought that the larger cations (Rb + , Cs + ) have a more favourable interaction with higher molecular weight oligomers of these polymers, resulting in an apparent shift in the MW distribution.In the present study, both MALDI and ESI-MS are used with the aim of establishing which cations interact favourably with polystyrene and whether the observed molecular weight distributions vary with the cation used. EXPERIMENTAL Mass spectrometryAll ESI experiments were carried out in a Quattro II (Micromass, Manchester, UK) tandem quadrupole instrument (Q 1 hQ 2 , where h is a hexapole collision cell) fitted with an electrospray source. The sampling cone potentials used in this study ranged from 90 to 180 V. It was generally found that, as the cone potential was increased beyond 150 V, the signal-to-noise ratio of the polystyrene ions increased significantly. Despite the high potentials applied to the cone, no fragmentation of the molecular ions was observed in the mass spectra. The spectra, from which molecular weight average values were calculated, were all acquired with the cone potential set at 180 V. The first quadrupole was scanned from m/z 3000-500 for a total of 20-30 scans. Ions, mass analysed by Q 1 , were detected by the first scintillator detector to generate the mass spectrum. All data were processed by means of the MassLynx data system. MALDI experiments were carried out in a TofSpec (Micromass, Manchester, UK) time-of-flight (TOF) instrument operated in reflectron mode. Ions generated in the source region, by means of a nitrogen laser * Correspondence to: M. J. Deery

show abstract

Section: Discussionmentioning

confidence: 99%

A Study of Cation Attachment to Polystyrene by Means of Matrix-assisted Laser Desorption/Ionization and Electrospray Ionization-Mass Spectrometry

Deery

Jennings

Jasieczek

et al. 1997

Rapid Commun. Mass Spectrom.

105

View full text Add to dashboard Cite

show abstract

“…It is shown that structural information on the polymer chain and end groups is best obtained by examining the fragment ion spectra of oligomers ionized by ammonium, alkali, and transition metal ions. T andem mass spectrometry using either matrixassisted laser desorption ionization (MALDI) or electrospray ionization (ESI) is being developed as a tool for polymer structural characterization [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. We are particularly interested in characterizing functional polyglycols, including poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and their copolymers [12][13][14][15][16][17][18][19].…”

mentioning

confidence: 99%

Characterization of poly(ethylene glycol) esters using low energy collision-induced dissociation in electrospray ionization mass spectrometry

Chen

2002

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

A method of characterizing polyglycol esters, an important class of industrial polymer, has been developed using electrospray ionization ion trap mass spectrometry (ESI ITMS). The fragmentation behavior of polyglycol esters is found to be different from that of polyglycols whose functional end groups are linked to the polymer chain via ether bonds (i.e., polyglycol ethers). The fragmentation pattern of an oligomer ion generated by low-energy collisioninduced dissociation is strongly dependent on the type of cation used for ionization. It is shown that structural information on the polymer chain and end groups is best obtained by examining the fragment ion spectra of oligomers ionized by ammonium, alkali, and transition metal ions. T andem mass spectrometry using either matrixassisted laser desorption ionization (MALDI) or electrospray ionization (ESI) is being developed as a tool for polymer structural characterization [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. We are particularly interested in characterizing functional polyglycols, including poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and their copolymers [12][13][14][15][16][17][18][19]. Structural characterization of this type of polymer is important because polyglycols are widely used in industry with their properties strongly depending on not only molecular weights, but also structures and compositions. Recently, polyglycols have also been increasingly used in biotechnical and biomedical applications such as the development of slow releasing drugs [20,21]. Traditionally, polyglycols were thought to be difficult to fragment in low-energy CID tandem MS. In our recent work, we demonstrated that lithium and transition metal ions could form adduct ions with polyglycol in ESI, and these adduct ions could readily undergo fragmentation [15,16]. The resulting fragment ion spectra were very informative for the structural characterization of polyglycol. Our previous study was focused on alcohol ethoxylates whose end-groups are linked to polyglycol chains via ether-type C™O bonds (i.e., polyglycol ethers). The results generated therein were compared to earlier studies of the same type of polyglycols employing fast atom bombardment (FAB) MS/MS by Latimer and coworkers [22][23][24][25].Poly(ethylene glycol) ester, especially fatty acid methyl ester ethoxylate (FAMEE), is another class of polyglycol which can be used as an alternative to alcohol ethoxylates in many industrial applications. With varying alkyl chain lengths in the fatty acid moiety, a wide range of hydrophilic lipophilic balance (HLB) values can be achieved to suit different applications [14]. They are extensively used as non-ionic bases for cosmetics and pharmaceuticals, non-ionic emulsifiers for vegetable and mineral oils, thickening agents for creams, anti-static agents for plastics, and non-ionic surfactants. Despite active MS study on alcohol ethoxylates [12][13][14][15][16][17][18][19], the literature on ester ethoxylates is scarce [5,16,63].In this work, we report a metho...

show abstract

“…In order to provide a complete description of the fragmentation routes of PVP even at the risk of being of limited use for the aged PVP samples but of de nite interest for the characterization of PVP samples generally speaking, a brief description of the behaviors of multiply charged adducts (ESI notoriously promotes the formation of multiply charged polymer ions 40,41) -the sample being preliminary SEC-fractionated to avoid any signal suppression e ect, Fig. S3) as well as PVP carrying alternative terminations is reported in the Supporting Information.…”

Section: Esi-ms N Of Sodiated Pristine Pvpmentioning

confidence: 99%

Multi-stage Mass Spectrometry of Poly(vinyl pyrrolidone) and Its Vinyl Succinimide Copolymer Formed upon Exposure to Sodium Hypochlorite

2016

View full text Add to dashboard Cite

e degradation routes of poly(vinyl pyrrolidone) (PVP) exposed to sodium hypochlorite (bleach) have been previously investigated using chemical analyses such as infrared spectroscopy. So far, no reports have proposed mass spectrometry (MS) as an alternative tool despite its capability to provide molecular and structural information using its single stage electrospray (ESI) or matrix assisted laser desorption ionization (MALDI) and multi stage (MS n ) con gurations, respectively. e present study thus reports on the characterization of PVP a er its exposure to bleach by high resolution MALDI spiralTOF-MS and Kendrick mass defect analysis providing clues as to the formation of a vinyl pyrrolidone/vinyl succinimide copolymeric degradation product. A thorough investigation of the fragmentation pathways of PVP adducted with sodium and proton allows one main route to be described-namely the release of the pyrrolidone pendant group in a charge remote and charge driven mechanism, respectively. Extrapolating this fragmentation pathway, the oxidation of vinyl pyrrolidone into vinyl succinimide hypothesized from the single stage MS is validated by the detection of an alternative succinimide neutral loss in lieu of the pyrrolidone release in the ESI-MS n spectra of the aged PVP sample. It constitutes an example of application of multi-stage mass spectrometry for the characterization of the degradation of polymeric samples at a molecular level.

show abstract

The fundamentals of applying electrospray ionization mass spectrometry to low mass poly(methyl methacrylate) polymers

Cited by 72 publications

References 25 publications

A Study of Cation Attachment to Polystyrene by Means of Matrix-assisted Laser Desorption/Ionization and Electrospray Ionization-Mass Spectrometry

A Study of Cation Attachment to Polystyrene by Means of Matrix-assisted Laser Desorption/Ionization and Electrospray Ionization-Mass Spectrometry

Characterization of poly(ethylene glycol) esters using low energy collision-induced dissociation in electrospray ionization mass spectrometry

Multi-stage Mass Spectrometry of Poly(vinyl pyrrolidone) and Its Vinyl Succinimide Copolymer Formed upon Exposure to Sodium Hypochlorite

Contact Info

Product

Resources

About